A generalised version of my previous answer...
#first add grouping variables
days <- 5 #grouping no of days
df$smalldaygroup <- c(0,cumsum(sapply(2:nrow(df),function(i) df$Day[i]!=df$Day[i-1]))) #individual days
df$bigdaygroup <- c(0,cumsum(sapply(2:nrow(df),function(i) df$Day[i]